This thesis will address the use of nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) techniques to probe the 'monolith reactor', which consists of a structured catalyst over which reactions may occur. This reactor has emerged as a potential alternative to more traditional chemical engineering systems such as trickle bed and slurry reactors. However, being a relatively new design, its associated flow phenomena and design procedures are not rigorously understood, which is retarding its acceptance in industry. Traditional observations are unable to provide the necessary information for design since the systems are opaque and dynamic. Therefore, NMR is proposed as an ideal tool to probe these systems in detail. The theory of NMR is summarised and the development of novel NMR techniques is presented. Novel techniques are validated in simple systems, and tested in more complex systems to ascertain their quantitative nature, and to find their limitations. These techniques are improvements over existing techniques in that they either decrease the acquisition time (allowing the observation of dynamically-changing systems) or allow us to probe systems in different ways to extract useful information. The goal of this research is to better understand the flow phenomena present in such systems, and to use this information to design better, more efficient, more controllable industrial reactors. The analysis of the NMR data acquired is discussed in detail, and several novel image-processing techniques have been developed to aid in the quantification of features within the images, and also to measure quantities such as holdup and velocity. These novel techniques are validated, and then applied to the systems of interest. Various configurations of monolith reactor, ranging from low flow rate systems to more challenging (and more industrially relevant) turbulent systems, are probed using these methods, and the contrasting flow phenomena and performance of these systems are discussed, with a view to optimisation of the choice of design parameters.